High molecular weight,high unsaturation c4-c10 isoolefin conjugated diene copolymers

ABSTRACT

SUBSTANTIALLY GEL-FREE, HIGH MOLECULAR WEIGHT, HIGH UNSATURATION COPOLYMERS OF ISOBUTYLENE AND CONJUGATED DIENES HAVING A NUMBER AVERAGE MOLECULAR WEIGHT OF AT LEAST 120,000 AND A MOLE PERCENT OF UNSATURATION OF AT LEAST 5% AND THE PROCESS FOR PREPARING SAID POLYMERS WHICH COMPRISES CARRYING OUT THE POLYMERIZATION IN A HOMOGENOUS PHASE, INTRODUCING THE CATALYST COMPRISING AN ALUMINUM HALIDE TO THE SYSTEM IN A SOLUBLE FORM AND CARRYING THE REACTION OUT AT A TEMPERATURE OF LESS THAN -100*C.

Apnl 30, 1974 w. A. THALER ETAL 3,808,177

HIGH MOLECULAR WEIGHT, HIGH UNSATURATION ISOBUTYLERE-CONJUGATED DIENE COPOLYMERS Filed June 8, 1971 9 Sheets-Sheet 1 Figure l APPROXIMATE CRITICAL HOMOGENEOUS POLYMERIZATION TEMPERATURES (ISOBUTYLENE-ISOPRENE COPOLYMERIZATION) 7OI|II'II|II.I||

SOLUBLE v POLYMER COOLING TEMPERATURE (C) 1 I I 1 1 I O 5 IO I5 20 25 3O 35 4O 5O 6O VOLUME ISOPRENE IN FEED (B) M. Thu/er J Pke r INVENTORS Filed June 8,

w. A. THALER ET AL 3,808,177

HIGH MOLECULAR WEIGHT, HIGH UNSATURAK ION ISOBUTYLENE-CONJUGATED DIEN-E COPOLYMERS 9 Sheets-Sheet 2 Figure 2 EFFECT OF COSOLVENT CONCENTRATION ON NUMBER AVERAGE MOLECULAR WEIGHT 200 I I I I I I I I I I I80 n-PENTANE CS F I CYCLOHEXANE BIS I60 METHYLCYCLO- I HEXANE I50 ISOPENTANE C I5 I IOO 50 l I I I I I I I- I I I O 5 IO I5 2O 3O 4O 5O 6O COSOLVENT come.

(VOLUME I4. Tho/er JP/(ennedy INVENTORS DJBUC/f/Gy Apnl 30, 1974 w. A. THALER EI'AL 3,808,177

HIGH uowcumm WEIGHT, HIGH unsmumu 10R I SOBUTYLENE-COHJ UGATED DIENE COPOLYMERS Filed June 8, 1971 9 Sheets-Sheet 5 Figure 3 INFLUENCE OF TEMPERATURE ON MOLECULAR WT.

I 20% n -HEPTANE COSOLVENT FOR A Bl5 ISOBUTYLENE-ISOPRENE COPOLYMER Ill'l I l,l-I l 1 I0 I l l l l I l l l l l 1 AVERAGE REACTOR TEMPERATURE I/T,KXIO

W. Thu/er .1 P/(ennedy INVENTORS D. .Buck/ey BY ATTORNEY A ril 30, 1974 Filed June 8, 1971 MOONEY VISCOSITY AT 2I2F,I ARGE ROTOR,8MIN.READING W. A. THALER ETAL HIGH MOLECULAR WEIGHT. HIGH URSATURATION ISOBUTYLENE-CONJUGATED DIENEI COPOLYMERS Figure 4 9 Sheets-Sheet 4 MOONEY VISCOSITY VERSUS NUMBER AVERAGE MOL.W.T.

ISOBUTYLENE-ISOPRENE COPOLYMER (CO I2 mOI "/OUNSATURATIONI III'I I l I l l l I l I l l 80 I00 I20 I40 NUMBER AVERAGE MOL. WT. x 10' W 7' ha/er JP/(enhea'y INVENTORS Q J Buckley /l I ""V 5 L'ILLLLW' 1 HA; 7 A TO NEY April 30, 1974 r w. A. THALER ETAL 3,808,177

HIGH MOLECULAR WEIGHT HIGH UNSAIURAI'ION ISOBUTYLENE-CONJUGATED DIENE COPOLYMERS Filed June '0, 1971 9 SheetsShe0t s Figure 5 EFFECT OF Kin ON TENSILE STRENGTH 5 2000 a w z LLI a: (I)

LIJ g I Mc=constant (adjusted curing times) i000 Q Constant curing times- 30'/290F- Mc Variable Constant curing times-.207 290F Mc Variable O Q l f I W Tim/er v J R/(ennedy INVENTORS DJBup/r/ egy LL; 3 -1. H4! BY /.ATI0R. v

Apnl 30, 1974 w. A. THALER ETAI. 3,808,177

HIGH MOLECULAR WEIGHTI HIGH UNSATURATION ISOBUTYLENE-CONJUGATED nmma COPOLYMERS Filed June 5, 1971 9 Sheets-$heet 6 Figure 6 PERMEABILITY TO AIR OF lSOBUTYLENE-ISOPRENE COPOLYMERS 25 I I I I I l I v l I PERMEABILITY(SCF curlin /day) QxIo o 20 r 40 so so Ioo ISOPRENE (MOLE WT/m/er JP/(ennedy INVENTORS QJBuck/ey I. i 71}: ,5

BY f ATTORNEY Apnl 30, 1974 w. A. THALER ETAL' 3,808,177

HIGH MOLECULAR WEIGHT, HIGH UNSATURA'IION ISOBUTYLENE'CONJUGATED DIENE COPOLYMERS Filed June 8, 1971 9 Sheets-Sheet. 7

Figure 7 PERMEABILITY AS A FUNCTION OF DIOLEFIN CONTENT OF AN ISOBUTYLENE COPOLYMER 5 I I r I l a S I N\ 4 ISOPRENE .5 0R g PIPERYLENE u. 3

I0 3 9 T x O 3 2 E p o |8/o C D AND 8 /o m w 2 TERPOLYMER (ISOPRENE OR PIPERYLENE) A II U-l CYCLOPENTADIENE o 1 l I l l o 20 40 so DIOLEFIN (MOLE WT/m/er J Pkennedy INVENTORS v DJBuc/r/py Y ATTORNEY Apnl 30, 1974 w. A. THALER ET AL 3,808.17?

HIGH MOLECULAR WEIGHT, HIGH UNSATURATION ISOBUTYLENE-CONJUGATED DIENE COPOLYMERS Flled June 8, 1971 I 9 Sheets-Sheet -3 25:00am 2 m2; wzci wmomo om 0w 9. ow on ow on ON 0. o

W 7' Ila/er JP/(ennedy INVENTORS D. J Buckley Sr.

' ATTORNEY United States Patent M HIGH MOLECULAR WEIGHT, HIGH UNSATURA- TION C C ISOOLEFIN CONJUGATED DIENE COPOLYMERS Warren A. Thaler, Matawan, and Donald J. Buckley, Plainfield, N.J., and Joseph P. Kennedy, Akron, Ohio, assignors to Esso Research and Engineering. Company Filed June 8', 1971, Ser. No. 151,038 Int. Cl. C081 1/72, 15/04, 15/40 US. Cl. 26080.7 59 Claims ABSTRACT OF THE DISCLDSURE BACKGROUND OF INVENTION Polymers and copolymers of isobutylene are well known in the art. In particular, copolymers of isobutylene with conjugated multiolefins have found wide acceptance in the rubber field. These polymers are generally termed in the art butyl rubber. The preparation of butyl rubber is described in US. Pat. 2,356,128, Which is incorporated herein by reference.

The term butyl rubber as employed in the specification is intended to include copolymers made from the polymerization of a reaction mixture comprising an isoolefin having about 4 to 7 carbon atoms, e.g. isobutylene and a conjugated multiolefin having about 4 to 14 carbon atoms, e.g. isoprene. Although these copolymers are said to contain about 0.2 to about 15% combined multiolefin, in practice the butyl rubber polymers of commerce contain about 0.6 to about 4.5 Wt. percent of multioolefin; more generally, about 1.0 to about 1.8 wt. percent, the remainder of the polymer being comprised of the isoolefin component.

Etforts to prepare isoolefin-multiolefin polymers of high unsaturation have met with varying degrees of success. Where substantially gel-free polymers have been prepared containing more than about multiolefin, the polymers have been of low number average molecular weight. This has been true even where these polymers had high viscosity average molecular Weights. In general, however, the products formed by prior art processes are either high in gel content or low in number average molecular weight and of little utility. In order to have practical commercial utility as a synthetic rubber, the isobutylene-multioolefin copolymers must be substantially gel-free and have a number average molecular weight of at least 120,000.

Multiolefins are known to be molecular weight and catalyst poisons; furthermore, increased unsaturation in the polymer backbone provides potential sites for gelation. Hence, attempts to prepare more highly unsaturated isoolefin-multiolefin copolymers by prior art methods have 3,808,177 Patented Apr. 30, 1974 resulted in the formation of either low molecular weight or resinous cross-linked polymers which have little or no commercial utility as elastomers.

Although some commercial elastomers such as styrene butadiene rubber or EPDM may contain as much as 2 to 9% gel, isobutylene copolymers of commerce are substantially gel free. The isobutylene copolymers may contain as much as 2% gel but preferably contain less than 1% There are numerous :patents and literature disclosures which generally disclose polymers and copolymers of isobutylene the copolymers purportedly having from about .5 to 98% unsaturation. Where the prior art copolymers are high in unsaturation, however, they are either low in number average molecular weight or resinous.

Japanese Pat. JA27416/ 68 published Nov. 26, 1968 teaches a process for preparing copolymers of conjugated diene compounds with isobutylene which contain a large amount of conjugated diene compounds using catalysts prepared by reacting (l) mercuric halide, aluminum halide or hydrogen halide, (2) zirconium halide and (3) aluminum metal in the presence of an aromatic compound, e.g. benzene. These products are described as copolymers which are rubbery substances when the isobutylene is high and are resinous When the isobutylene content is low. The resinous properties result from gelation and crosslinking of the polymer during its preparation. These gelled and crosslinked products have little utility as rubbers. The products of lower unsaturation, i.e. high isobutylene content rubbers, are of the conventional butyl rubber type.

Japanese Pat. JA27417/ 68 published Nov. 26, 1968 teaches a method for preparing copolymers of dienes and isoolefins containing about 0.1 to about 40 wt. percent, preferably about 0.5 to 5 wt. percent of diene. The polymers are :prepared using a catalyst derived from (1) metal oxides of the general formula M O wherein M is nickel or cobalt and 1 y/x 1.5, and (2) aluminum halide. Again, the low unsaturation polymers are the conventional butyl rubbers whereas the highly unsaturated materials are either low in number average molecular weight or are gelled polymers.

US. Pat. 3,356,661 teaches a method for preparing copolymers of isobutylene and butadiene-1,3 hydrocarbons, for example copolymers of isoprene and isobutylene. The copolymers produced by the process disclosed are either lower molecular weight, i.e. less than 100,000 viscosity average molecular Weight or gelled polymers.

US. Pat. 3,165,503 teaches a method for polymerizing butadiene-1,3 hydrocarbons, e.g., isoprene. The invention of this patent is directed primarily towards the preparation of :polyisoprene. However, copolymers of isoprene and isobutylene are disclosed. The preferred copolymers are said to contain from about 1 to 50 wt. percent of butadiene-1,3 hydrocarbon units. Hydrocarbon copolymers of isoolefin and conjugated dienes prepared by the method taught by the patentee are found to be low in number average molecular weight or gelled polymers.

US. Pat. 3,466,268 and its parent counterpart, US. 3,357,960 disclose a butadiene isobutylene copolymer and a process for preparing said copolymer. The invention disclosed is a method of improving butadiene polymers by incorporating in the structure varying amounts of isobutylene. Preferably, the amount of isobutylene incorporated is said to be about 2 to 40 wt. percent. The polymers disclosed are generally low in number average molecular weight. Substitution of isoprene for butadiene results in highly crosslinked copolymers which have little utility.

U.S. Pat. 2,772,255 (Br. 744,514) discloses a method for preparing high molecular weight butyl rubbers. In general, the polymers which are prepared are conventional butyl rubbers having less than 3 mole percent unsaturation. Attempts to produce butyl rubber type polymers having unsaturation in excess of 5 mole percent unsaturation result in products which either are low in number average molecular weight or are gelled and highly crosslinked.

High unsaturation isobutylene-isoprene copolymers have been prepared (see, for example, U.S. Pat. 3,242,147 incorporated herein by reference). Although these polymers are purportedly high in viscosity average molecular weight, the number average molecular weights are low. Hence, the products have little commercial significance.

Unlike plastics, elastomers require a high number average molecular weight in order to realize desirable levels in physical properties. For example, tensile strength for elastomers is critic-ally dependent on number average molecular weight since these polymers are used well above their glass transition temperature and are generally amorphous.

'In contrast to elastomers, plastics are used Well below their glass transition temperature and it is molecular associations which gives them their structural integrity. As a result, number average molecular Weights in the order of 10,000 to 70,000 are adequate for commercial utility.

Elastomers, on the other hand, obtain their structural integrity from -a crosslinked network. Perfection of this network is directly dependent on the length of the polymer molecules from which the network is derived. Number average molecular weight (Mn) is a measure of the length of the molecules. Viscosity or weight average molecular weights are misleading measurements since their numerical value is greatly affected by small variations in the distribution of the higher molecular weight fractions. Hence, polymers of low number average molecular weight may have high viscosity average molecular Weight as a result of disproportionate distribution of the high molecular weight fraction.

The importance of number average molecular weight on tensile strength has long been recognized (see, for example, Flory, p. 5, Ind. Eng. Chem., 38, 417 (1946), incorporated herein by reference. Flory showed that for low unsaturation elastomeric copolymers of isobutylene tensile strength increased rapidly as the number average molecular weight was increased beyond a minimum value (i.e..100,000) then approaches an asymptotic limit.

For economic reasons, oil extendability is an essential characteristic of a commercial elastomer for almost all major uses. The tensile strength of butyl rubber vulcanizates is reduced by the addition of oil, and to retain the original tensile strength of the undiluted composition it is necessary to increase the number average molecular weight. Oil extension also improves the low temperature properties of butyl innertubes and when this phenomenon was discovered, it was necessary to develop higher molecular weight polymers to accommodate the added oil. See, for example, Buckley et al., Ind. Eng. Chem, 42, 2407 (1950).

This finding resulted in the rapid adoption by industry of the high molecular weight type of butyl GR-l18 with Mooney viscosity greater than 71 (212 F.). These materials generally have number average molecular weights of 150,000 or greater. In contrast, the previously used polymers which have number average molecular weights of less than 120,000 with Mooney viscosity specification of 38-49 (212 F.) were limited to applications which did not require oil extension, and today represents a very minor portion of the butyl rubber market having, been supplanted almost entirely by the higher molecular weight butyl rubbers.

Although it has been postulated that higher unsaturation copolymers of isobutylene would be attractive polymers, useful polymers have not been available since the prior art methods are not capable of producing highly unsaturated, e.g., at least 5 mole percent to about 40 mole percent, isobutylene copolymers of sufiiciently high number average molecular weight, e.g., at least 120,000. Hence, the prior art isobutylene-conjugated diene copolymers offered commercially are low in unsaturation, e.g., 1-4.5 mole percent.

Hence, heretofore, methods of preparing copolymers of isoolefins and conjugated dienes have not included a means for making commercial quality elastomers containing greater than 5 mole percent diene. To be of commercial quality the elastomer must be substantially gel free and have a number average molecular weight (Mn) of at least 120,000.

Although the isobutylene-conjugated dienes of commerce have improved ozone resistance, these polymers are still subject to ozone cleavage since the site of unsaturation is in the polymer backbone. It has been postulated that isobutylene copolymers having unsaturation on the side chain rather than the backbone would be highly resistant to ozone attack. Attempts to produce such polymers using cyclopentadiene as the diene comonomer have been notably unsuccessful.

Isobutylene-cyclopentadiene copolymers of the prior art have been too low in molecular weight to be of commercial significance. Some improvement in molecular weight has been accomplished by copolymerizing isobutylene with minor amounts of cyclopentadiene (CPD) along with other monomers including crosslinking agents such as divinyl benzene. The resulting products are somewhat improved terpolymers or tetrapolymers resulting from the linking of the low molecular weight isobutylene-CPD chains into two dimensional highly branched polymers. Such polymers, however, have inferior physical properties as compared to the butyl rubbers of commerce and hence have not gained acceptance.

A review of the art illustrates the problems encountered where attempts were made to prepare copolymers of isobutylene and cyclopentadiene (CPD). For example, U.S. Pat. 2,577,822, incorporated herein by reference, teaches the need for the addition of divinyl benzene in order to compensate for the deleterious effect of CPD on molecular weight.

U.S. Pat. 3,080,337, incorporated herein by reference, teaches the addition of isoprene as a third monomer but the resulting products are low in unsaturation and have poor physical properties. Others have made various attempts to produce CPD isoolefin copolymers with varying degrees of success; see, for example, U.S. Pats. 3,239,- 495; 3,242,147; 2,521,359; British Pat. 1,036,618 and I & EC Frod R and D 1, 216-20 (1962) incorporated herein by reference. These polymers, however, have substantially no commercial significance because, even when only minor amounts of CPD were present, they are low in num ber average molecular Weight.

SUMMARY OF INVENTION It has surprisingly been found that substantially gelfree copolymers of isoolefins and conjugated diolefins having a mole percent unsaturation of at least 5% and a number average molecular weight (lTIn) of at least 120,000 may be prepared by carrying out the polymerization in the presence of not more than about 40 wt. percent, based on the total monomers plus cosolvent, of a cosolvent which is a solvent for the polymer at the polymerization temperature and carrying out the reaction at a temperature of less than C. The catalyst must be an alumi num halide and must be introduced into the reaction zone dissolved in a polar solvent.

The quantity of cosolvent used is kept to a minimum in order to maximize molecular weight. The optimum cosolvent level is determined by selecting the minimum solvent-monomer ratio at which the copolymer to be prepared remains in solution at the polymerization temperature.

Surprisingly, the process of this invention makes it possible to prepare isobutylene-cyclopentadiene (CPD) copolymers of high number average molecular weight. Terpolymers of isobutylene, CPD and a third conjugated multiolefin have unexpected ozone resistance.

BRIEF DESCRIPTION OF DRAWINGS FIG. I is a plot of the critical homogeneous polymerization temperature as a function of multiolefin content.

FIG. II is a graphical representation of the effect of cosolvent concentration on number average molecular weight.

FIG. III is a graphical representation of the effect of polymerization temperature on molecular weight.

FIG. IV is a graphical representation of the relationship between Mooney viscosity and number average molecular Weight for isobutylene-isoprene (B15) copolymers.

FIG. V is a graphical representation of the effect of number average molecular Weight on tensile strength.

FIG. VI is a graphical representation of the permeability to air of isobutylene-isoprene copolymers as a function of isoprene content.

FIG. VII is a graphical representation of the permeability to air of various copolymers and terpolymers as a function of multiolefin content.

FIG. VIII is a graphical representation of the crosslink concentration as a function of cure time for various copolymer compositions.

FIG. IX is a graphical representation of the effect of multiolefin content on vulcanization characteristics.

DETAILED DESCRIPTION This invention relates to a method of preparing substantially gel-free copolymers of an isoolefin and a conjugated multiolefin wherein said copolymers have a number average molecular weight of at least 120,000 and a mole percent unsaturation of at least 5%. The preferred polymers of this invention have a number average molecular Weight of at least 130,000; more preferably at least 140,000; most preferably 150,000; e.g., at least 160,000.

In the preparation of the copolymers of this invention any cationically polymerizable multiolefin may be copolymerized with a cationically polymerizable isoolefin.

The isoolefins suitable for use in the practice of the inventions are preferably hydrocarbon monomers having about 4 to about carbon atoms. Illustrative nonlimiting examples of these isoolefins are isobutylene, 2-methyl-lbutene, 3-methyl-1-butene, 4-methyl-1-pentene, beta-pinene, etc. Preferably, the isoolefin is isobutylene.

The multiolefins suitable for use in this invention are conjugated hydrocarbon multiolefins having 5 to about 14 carbon atoms; more preferably, the multiolefins are conjugated diolefins of 5 to 9 carbon atoms. Illustrative nonlimiting examples of these multiolefins are isoprene, piperylene, 2,3-dimethyl butadiene, 2,5-dimethylhexadi-2,4-ene, cyclopentadiene, cyclohexadiene, methylcyclopentadiene, fulvene, etc.

In order to obtain number average molecular weights of at least 120,000, the reaction must be carried out below -100 C., preferably about '110 to 140 C., more preferably about 110 C. to about -35 C., most preferably about --115 to -130 C., e.g. 120 C. To obtain the desired number average molecular Weight in a substantially gel-free polymer, a homogeneous polymerization is required. This is achieved by carrying out the reaction in a vehicle which is a solvent for the copolymer at the reaction temperature. The vehicle comprises predominantly the monomers to be polymerized in conjunction with an inert cosolvent or mixtures of inert cosolvents. The vehicle (monomers plus cosolvent) must of course be liquid at the polymerization temperature.

It is essential in carrying out the process of this invention that the cosolvent comprise at least 5% by volume and not more than 40% by volume of the total cosolventmonomers system. Preferably, about 5 to about 30 volume percent cosolvent is used; more preferably about 7.5 to 25 volume percent, most preferably about 10 to about 20 volume percent, e.g., 15 volume percent.

The optimum amount of cosolvent to be used is the minimum amount necessary to avoid gelation. If too little cosolvent is used gelation of the product results. Too high a level results in undesirable lowering of number average molecular weight.

For the purposes of this invention, it is convenient to define the volume percent of inert cosolvent as that calculated based on the volume of monomers at the polymerization temperature while the volume of cosolvent is determined at 25 C. The volume percent of cosolvent as calculated is uncorrected for volume changes and cooling of the cosolvent to reaction conditions.

The minimum quantity of a given cosolvent required to produce gel-free polymers is a function of the cosolvent, the conjugated multiolefin used and the polymerization temperature. Having selected the composition of the blend of monomers and the cosolvent to be used the minimum quality of cosolvent required is readily determined by carrying out the polymerization using varying amounts of cosolvent. The minimum quantity of cosolvent necessary is that amount required to maintain a homogeneous system; that is to prevent precipitation of polymer during polymerization.

The term cosolvent as used in the specification and claims means the inert solvent which, together with the monomer feed, comprises the vehicle for the reaction. The cosolvent and monomers must be mutually soluble and the blend of monomers plus cosolvent must be a solvent for the copolymer at the polymerization temperature. The term inert means that the cosolvent will not react with the catalyst or otherwise enter into the polymerization reaction. The cosolvent must not contain substituents in its molecule which will interfere with the polymerization reaction. Aliphatic hydrocarbons are suitable cosolvents. The preferred cosolvents are parafiinic hydrocarbons, and carbon disulfide. Preferably, the paraffinic hydrocarbon solvent is a C -C hydrocarbon, more preferably a C to C hydrocarbon. Illustrative examples of the hydrocarbon solvents are pentane, isopentane, methyl pentane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, heptane, isooctane, 1,2,3,3-tetramethyl hexane, tetramethyl cyclohexane, etc. Generally any paraffin, whether normal, branched or cyclic which is a liquid under polymerization conditions, may be used. The term paraffin as used in the specification and claims includes normal paraffins, cycloparafiins and branched paratfins.

It will be evident to those skilled in the art that since the monomers act as part of the solvent system for the polymer, the conversion level of the polymerization must not be so great as to result in precipitation of the copolymer as a result of depletion of solvent. Preferably the conversion level is about 2 to about 20% more preferably about 3 to 15%; most preferably about 5 to about 13%, e.g., 10%.

In the practice of this invention the catalyst must be an aluminum halide. Furthermore, the catalyst must be in the form of a homogeneous solution or submicron dispersion of catalyst particles, e.g., colloidal dispersion. Therefore, the catalyst must be dispersed or dissolved in a suitable catalyst solvent or mixture of solvents. The catalyst solvent must be a polar solvent. Illustrative examples of suitable aluminum halides are AlCl and AlBr The preferred catalyst is aluminum chloride.

The term polar solvent as used in the specification and claims means non-aromatic, organic solvents having a dielectric constant at 25 C. of at least 4, preferably about 4 to about 20, more preferably about 6 to about 17; most preferably about 9 to about 13. These polar solvents, however, must not contain sulfur, oxygen, phosphorus or nitrogen in the molecule since compounds containing these elements will react with or otherwise deactivate the catalyst.

The preferred polar solvents are inert halogenated aliphatic hydrocarbons; more preferably halogenated paraffinic hydrocarbons and vinyl or vinylidene halides; most preferably primary or secondary chlorinated paraffinic hydrocarbons. The halogenated hydrocarbon is preferably a C C paraffin hydrocarbon; more preferably a C -C parafiin. The ratio of carbon atoms to halogen atoms in the polar solvent is preferably 5 or less. Preferably the halogen is chlorine.

Illustrative examples of these polar organic solvents are methylchloride, ethyl chloride, propyl chloride, rnethyl bromide, ethyl bromide, chloroform, methylene chloride, vinyl chloride, vinylidene chloride, dichloro ethylene, etc. Preferably, the polar solvent is methyl chloride or ethyl chloride. Generally any inert halogenated organic compound which is normally liquid under polymerization conditions and has a dielectric constant of at least 4.0 may be used.

It is essential in carrying out this invention that the aluminum halide catalyst be in solution in the polar organic solvent prior to introduction of the catalyst to reaction medium. Combining the polar organic solvent with the reaction medium and thereafter adding the aluminum halide catalyst thereto will not result in the production of the high fin, high unsaturation polymers of this invention.

Use of the term solution with reference to the polar organic solvent/aluminum halide systems is intended toinclude both true solutions and colloidal dispersions since they may exist concurrently in the same system.

The aluminum halide/polar solvent catalyst preferably comprises about 0.01 to about 2 weight percent aluminum halide; more preferably about 0.05 to about 1; most preferably 0.1 to about 0.8.

In carrying out the polymerization of this invention those skilled in the art will be aware that only catalytic amounts of catalyst solution are required. Preferably the volume ratio of monomer plus cosolvent to catalyst solution is about 100/ l to about 9/ 1; more preferably about 80/1 to about 10/ 1; most preferably about 50/1 to about 20/1.

In practicing the process of this invention, it is essential that the polymerization be carried out in the homogeneous phase without the precipitation of polymer. Conventional slurry processes are inapplicable for the preparation of the high unsaturation polymers of this invention since by their nature they result in polymer precipitation with gelation of the polymer as a consequence.

The amount of cosolvent required in order to maintain the polymerization reactants and product in solution throughout the polymerization is a function of the multiolefin selected for polymerization and its concentration in the monomer feed. The polymerization temperature at which precipitation of polymer will occur is itself a function of the amount of and type of cosolvent and the particular multi-olefin being copolymerized.

The term critical homogeneous polymerization temperature as used in the specification and claims means that polymerization temperature below which precipitation of polymer will occur when no cosolvent is included in the reaction mixture, i.e., the only solvent for the reactants and product being the monomer feed.

Referring now to FIG. I, the volume percent of multiolefin (isoprene) in the monomer blend (B#) is plotted as a function of the polymerization temperature below which precipitation of polymer and as a consequence gelation occurs in the absence of cosolvent. The curve represents the critical homogeneous polymerization temperatures for isobutylene-isoprene systems.

The process of this invention incorporates the isobutylene and isoprene into the copolymer in substantially the same ratio as it exists in the feed. For example, where an isobuylene-isoprene monomers feed comprises 15 volume percent isoprene the polymer formed therefrom comprises about 12.5 mole percent unsaturation. Characterization of polymers prepared by bulk polymerization, i.e., without cosolvent, shows that the polymers formed are low in number average molecular weight (Mn). In order to increase Mn, the lowering of polymerization temperature is an obvious expedient. However, in the absence of cosolvent, the result is not greater Mn but gelation.

With reference to blend of monomers or blend of monomers from which polymers have been made, the term B# means the volume percent isoprene in the monomer blend at the polymerization temperature. For example, a B15 polymer is a polymer prepared from an isobutylene-isoprene blend comprising 15 volume percent isoprene. As has been indicated earlier the mole percent unsaturation is generally substantially the same as the B#.

The terms unsaturation or multiolefin content as used with reference to the amount of multiolefin enchainment in the product are equivalent terms. The composition of the copolymer (mole percent unsaturation=mole percent diene content) is substantially the same as the composition of the feed for acyclic dienes. However, where the diene is a cyclic diene it is present in considerably higher amounts, e.g., 3 to 4 times, in the copolymer as in the feed.

The problem of gelation is obviated by the addition of a cosolvent which permits the lowering of polymerization temperature below the critical homogeneous polymerization temperature. It has been found that polymerization temperature of at least C. is necessary in order to achieve fin values of at least 120,000. At least 5 volume percent inert solvent based on the monomer feed is necessary in order to carry out the polymerization in solution at these low temperatures.

The polymers of this invention have lTn of at least 120,000. Preferably the Mn is at least 130,000; more pref erably at least 140,000; most preferably at least 150,000, e.g., 160,000.

In practicing the process of this invention, one skilled in the art may proceed as follows in order to determine the preferred reaction conditions.

First, a convenient polymerization temperature below 100 C. is selected. Preferably the temperature is below C., e.g., C. Next the desired feed composition, i.e. monomers and ratio of isoolefin to multiolefin and the cosolvent to be used are selected. Polymerization reactions are carried out using successively greater amounts of solvents. The initial polymerization reaction is carried out using 5 volume percent based on the total of monomer plus solvent of the cosolvent since lesser amounts will be inadequate. In each successive run an additional 5 volume percent is added. The procedure is continued until the reaction medium remains clear throughout the reaction. Turbidity is indicative of precipitation of polymer which leads to gelation.

The polymer formed is characterized for Mn and mole percent unsaturation. Where a higher Mn is desired it may be achieved by either lowering the polymerization temperature or where possible using slightly less solvent than determined by the above method, e.g., 1-2 vol. percent less, provided that turbidity does not occur. Reduction of polymerization temperature may result in a greater cosolvent requirement. Hence, the aforegoing procedure of adding additional solvent to the reaction medium must be continued until the reaction medium is again clear throughout the polymerization.

Where the mole percent unsaturation is to be adjusted somewhat more or less of the mutliolefin is used depending on whether a slightly higher or lower unsaturation is desired. Change in feed composition may require readjusting the cosolvent requirement. Generally, increasing the multiolefin content of the monomer feed decreases the cosolvent requirements of the system.

Th optimum reaction conditions are those which give the maximum Mn at the highest temperature for the desired unsaturation level. The smaller the quantity of cosolvent used the greater the fin. Economic considerations dictate the use of the warmest temperature practical for polymerization. Use of lower temperatures will necessitate the use of greater amounts of cosolvent. At temperatures below 140 C. the cosolvent requirements for homogeneous polymerization are so great that further reduction in temperature result in lower rather than higher fin as a result of the larger quantities of solvent required.

Where it is anticipated that products of different mole percent unsaturation are to be produced it may be advantageous to determine the critical homogeneous polymerization temperature curve for the isoolefin multiolefin system to be used.

In utilizing this approach, the desired isobutylene-multiolefin polymer to be prepared first is selected. A critical homogeneous polymerization temperature curve similar to FIG. 1 for the multiolefin selected is prepared using a polar solvent-catalyst system suitable for use in this invention.

In conducting the necessary polymerizations, the reactions are carried out in bulk without using inert diluent. For each different multiolefin content monomer feed, polymerizations are carried out at progressively lower temperatures until the critical homogeneous polymerization temperature for the feed composition is determined. The polymerization is repeated for different feed compositions and the data obtained are the critical homogeneous polymerization temperatures as a function of multiolefin content of the feed. A plot of these data gives the critical homogeneous polymerization temperature curve analysis to that of FIG. 1. The polymer formed is analyzed for multiolefin content and a determination is made of the corelation mole percent unsaturation in the polymer and volume percent multiolefin in the feed.

The polymer formed in bulk polymerization is unsuitable for commercial use since it has a Mn of less than 120,000. In order to increase the Mn of the poly-mer it is necessary to carry out the polymerization at lower temperatures, e.g., less than 1000 C., which requires the addition of cosolvent to prevent precipitation of polymer during polymerization.

The quantity of cosolvent used should be kept to a minimum since excess cosolvent results in the lowering. of fin. In determining the amount of solvent to be used the monomer feed composition is determined. A convenient polymerization temperature below -100 C. is selected. As a first approximation the volume percent of inert solvent to be added to the monomer feed is the difference between the multiolefin content of the feed and the multiolefin content of a monomer feed having a critical homogeneous solution temperature which is the same as the polymerization temperature to be used. For example, an isobutylene copolymer is to be prepared using isoprene as the multiolefin. The monomer feed is to contain multiolefin and polymerization is to be carried out at 105 C. Referring to FIG. 1, the isobutylene-isoprene composition having a critical homogeneous solution temperature of -105 C. contains 35 volume percent isoprene. Hence, as a first approximation, the volume percent cosolvent to be used in the polymerization of a feed containing 15 volume percent isoprene is 35 minus 15 or volume percent cosolvent. The fin of the polymer formed may be increased by either reducing the polymerization temperature or reducing the amount of solvent,

10 provided, however, neither the temperature nor solvent may be reduced to the level where precipitation of polymer occurs.

Alternately, the minimum cosolvent requirements for a particular isoolefin-multiolefin may be determined by carrying out the polymerization at the critical homogeneous polymerization temperature for the isoolefin-multiolefin feed composition, terminating the polymerization be destroying the catalyst and, with constant stirring, lowering the temperature of the system to the desired polymerization temperature. The polymer which, of course, is by definition insoluble below the critical homogeneous polymerization temperature will precipitate out and the system will appear turbid. The polymer will not be gelled, however, since polymerization was terminated prior to precipitation. The cosolvent selected is then added in incremental amounts until the turbidity disappears. The quantity of solvent so added is a good approximation of the minimum solvent requirements for a given isoolefin-multiolefin feed to be polymerized at a given temperature.

The term solution polymerization as used in the specification and claims means a polymerization carried out so that the polymer product remains dissolved throughout the reaction.

Where the diene to be polymerized is isoprene, the preferred cosolvents are heptane, hexane or methylcyclohexane utilized at about 5 to about 30 volume percent; more preferably at about 10 to about 25 volume percent, e.g., 10 volume percent. Where the diene is cyclopentadiene the preferred cosolvents are methylcyclohexane (MCH) and CS utilized at about 15 to about 30 volume percent, e.g., 20 to about 25 volume percent.

The products of this invention oifer a number of important advantages over the commercially available butyl rubbers. In addition, to possessing superior cold flow and green strength properties while retaining the low air permeability and mechanical damping characteristics of conventional low unsaturation isoolefin copolymers, the products of this invention offer greater versatility in vulcanization techniques. Furthermore while the vulcanization of conventional isoolefin-multiolefin copolymers requires the use of ultra-accelerator type cures, e.g., thiuram (Tuads) or dithiocarbamates (Tellurac), the products of this invention may be vulcanized using the thiazole, e.g., mercaptobenzothiazole, type cures currently used in the vulcanization of general purpose rubbers, e.g., natural rubber, SBR, polybutadiene, etc. Because of certain factors of which such a premature vulcanization (scorch) is a prime example, modern practice has tended towards the use of a special class of thiazoles called delayed action accelerators. These delayed action accelerators permit the processing of the compounded rubber (including vulcanizing agents) at the vulcanization temperature for a predetermined period of time before vulcanization commences. Such cure techniques are not possible with conventional isoolefin copolymers. The delayed action accelerators are, however, used advantageously in the vulcanization of the isoolefin copolymers of this invention.

The delayed action accelerators suitable for use in vulcanizing the products of this invention include the henzothiazole sulfenamides having the general formula wherein X is an amino group. The amino group is mono or diorganosubstituted and may be cyclic including heterocyclic. For example, X may be or '-NR where R is H or R and R is organo or cycloorgano. R is a divalent organo radical. Illustrative examples of X are cyclohexylamino, tertiary butyl amino, diisopropyl amino, dicyclohexyl amino, pentamethyleneamino, morpholino, 2-(2,6-dimethyl morpholino), etc. Specific illustrative examples of these sulfenamides are N,N-diethylbenzothiazole-2-sulfenamide, N-N-diisopropyl benzothiazole-Z-sulfenamide,

N-tertiary butyl benzothiazole-Z-sulfenamide, N-cyclohexyl benzothiazole-Z-sulfenamide, N,N-dicyclohexyl benzothiazol-Z-sulfenamide, 2-(morpholino) benzothiazole sulfenamide, 2-(2,6-dimethyl morpholino) benzothiazole sulfenamide, 2-piperidinyl benzothiazole sulfenamide.

In general, any benzothiazole sulfenamide may beu sed as a delayed action accelerator for the sulfur vulcanization of the polymers of this invention.

The delayed action accelerator is incorporated into the vulcanizable polymer composition at preferably about 0.1 to about 5 wt. percent based on the polymer; more preferably about 0.25 to about 3.5; most preferably about 0.5 to about 3.0 wt. percent, e.g., 0.5 to about 2.5 wt. percent.

It is, of course, obvious to those skilled in the art that the delayed action cures are sulfur cures and sulfur must be incorporated into the polymer blend either as elemental sulfur or as nonelemental sulfur. Suitable nonelemental sulfur is in the form of those compounds which will release sulfur to the polymer under vulcanization conditions. For a description of these nonelemental sulfur compounds, generally, see vulcanization of Elastomers, Ch. 4, I. C. Ambelang, Reinhold, New York, 1964 incorporated herein by reference. Illustrative examples of these nonelemental sulfur compounds are dimorpholvinyl disulfide and alkyl phenol disulfides. The term sulfur donor as used hereinafter in the specification and claims means elemental sulfur as well as the aforementioned nonelemental sulfur compounds. The quantity of sulfur donor required for vulcanization is well known to those skilled in the art. Where the sulfur donor is elemental sulfur, it is incorporated into the polymer at about 0.1 to about 5 wt. percent based on the polymer; more preferably about 0.25 to about 3.5 wt. percent most preferably about 0.5 to about 3.0 wt. percent, e.g., 0.5 to about 2.5 wt. percent. Where the sulfur donor is a nonelemental sulfur compound, it is incorporated at a weight percent of about three times that required for elemental sulfur. The term nonelemental sulfur compounds means organic compounds containing sulfur and capable of donating the sulfur to a vulcanization reaction, e.g., disulfides and polysulfides.

The delayed action accelerators may be modified by retarders and activators which will respectively retard or activate the sulfur vulcanization. The addition of the retarder will further delay the time at which vulcanization occurs while the activator will cause vulcanization to occur sooner, e.g., shorter delay time.

The retarders suitable for use in the practice of this invention include organic compounds having a pK of about 2 to less than 7; preferably about 3 to about 6.5; more preferably about 4 to about 6, e.g., 5. The term pK is the dissociation constant as measured in aprotic solvents, see for example Acid-Base Behavior in Aprotic Solvents NBS Monograph 105, August 1968.

The activators suitable for use in the practice of this invention are metallic oxides, hydroxides and alkoxides of Group Ia and Group IIa metals of the Periodic Table of the Elements and organic compounds having a pK of about 8 to about 14; preferably about 9 to about 12; more preferably about 9.5 to about 11, e.g., 10.

Illustrative examples of retarders are N-nitroso diphenylamine, N-cyclohexyl thiophthalimide, phthalic anhydride, salicylic acid, benzoic acid, etc. Generally, the preferred retarders are nitroso compounds, phthalimides, anhydrides and acids.

Illustrative examples of activators are Mg'O, diphenylquanidine, hexane-l-amine, 1,6-hexane diamine, sodium methoxide, etc. The preferred activators are quanidines and amines.

The retarders and activators are preferably incorporated into the polymer at about 0.1 to about 5 wt. percent; more preferably about 0.25 to about 3.5 wt. percent; most preferably about 0.5 to about 3.0 wt. percent, e.g., 0.5 to about 2.5 wt. percent.

Copolymers of isoolefins and cyclodienes, e.g., isobutylene and cyclopentadiene possess markedly improved resistance to degradation by ozone over the acyclic diene copolymers. Although it has been postulated that such copolymers would have such improved properties as a result of having the unsaturation located in a side chain rather than in the backbone, it has heretofore not been possible to prepare substantially gel-free isoolefin-cyclodiene copolymers of high number average molecular weight even at low levels of unsaturation.

Utilizing the process of this invention, it is now possible to prepare such cyclodiene copolymers having as little as 0.5 mole percent unsaturation and as high as 40 mole percent unsaturation. Preferably, the polymers contain about 3% to about 35%; more preferably about 6 to about 30 mole percent unsaturation; most preferably 12 to about 30 mole percent, e.g., 16 to about 28 mole percent. As a result of the relatively lower reactivity of the unsaturation as compared to the acyclic diene copolymers, copolymers having incorporated therein about 2-4 mole percent cyclic diene are about as reactive as butyl rubber having an acyclic diene content of about 0.5 to about 1.5 mole percent and require ultra acceleration for sulfur vulcanization. By contrast the higher unsaturation copolymers e.g. at least 5 mole percent, preferably at least 8 mole percent, may be sulfur vulcanized using the delayed action accelerator cure systems described above.

In general, the polymers of this invention must not contain more than 40 mole percent unsaturation. Above 40% unsaturation, polymers prepared from acyclic multiolefins are intractable and unstable, e.g., gel on standing. Where the multiolefin is a cyclic multiolefin above 40 mole percent unsaturation, the glass transition temperature of the polymer is too high. As a result, the polymers have poor low temperature characteristics. Preferably, the polymers of this invention have about 5 to about 35 mole percent unsaturation; more preferably about 8 to about 30 mole percent; most preferably about 10 to about 25 mole percent; e.g., 1 6 to about 25 mole percent.

As has been pointed out earlier the highly unsaturated polymers of this invention are substantially as impermeable to air as are commercial low unsaturates, e.g., 1.5 mole percent butyl rubbers. Surprisingly, isoolefin copolymers of CPD or terpolymers of an isoolefin-CPD and an acyclic diene are less permeable to air at the higher unsaturation levels than is the low unsaturation butyl rubber of commerce.

Thus, the process of this invention permits the preparation of isoolefin copolymers, heretofore unattainable, which surprisingly retain all the advantageous characteristics of conventional low unsaturation butyl rubber while exhibiting improved vulcanization characteristics and in some cases, e.g., CPD copolymers, improved ozone resistance and air impermeability.

The advantages of this invention may be more readily appreciated by reference to the following examples.

EXAMPLE 1 Monomer mixes comprising varying amounts of isoprene 1n isobutylene were polymerized using as the catalyst a solution of AlCl in methylchloride (about 0.5 g. AlCl 100 ml. of CH Cl). The reactions were permitted to proceed for 10 minutes and the catalyst deactivated with a few drops of 10% NaOCH in CH OH. The polymer was precipitated from boiling methanol saturated with PBN (N-phenyl-B-naphthylamine) Polymerization was carried out over a range of temperatures until that temperature at which polymer would fall out of solution was determined for a given isoprene/ isobutylene feed mixture.

The results are shown in FIG. 1. The critical temperature below which polymerization is no longer homogeneous (i.e. single phase solution) is shown as a function of isoprene content (B#) of the isoprene/isobutylene feed. In the area below the curve precipitation of polymer with subsequent gelation occurs. Above the curve polymerization is homogeneous and a soluble gel-free polymer is prepared.

The temperature for a given isoprene content of the monomer feed at which precipitation occurs is termed the critical homogeneous polymerization temperature" (CHPT) for the bulk polymerization (no inert cosolvent) of isobutylene-isoprene feeds. The CHPT is not a rigorously defined value but rather an operational quantity defining the lowest temperature at which gel-free polymerization can be carried out in bulk to significant conversion levels, e.g., 2% conversion.

EXAMPLE 2 Charges of monomer feed comprising 30 volume percent isoprene and 70 volume percent isobutylene were polymerized at the CHPT for that composition (100" C.) and at 120" C. The polymerization was initiated with AlCl as the catalyst dissolved in methyl chloride (ca. 0.5 g. AlCl 100 ml. CH Cl). The reaction was terminated ten (10) minutes after the introduction of catalyst using a few drops of a 10% solution of sodium methoxide in methanol saturated with PBN. The polymer was precipitated from methanol and dried in a vacuum oven at 50 C. The gel content of the polymers was determined by redissolving the polymers in toluene and separating the soluble polymer from insoluble gel. The results are shown in Table I.

TABLE I.BULK POLYMERIZA'IION OF ISOBUTYLENE- ISOPRENE FEED CONTAINING 30% ISOPRENE It is evident that carrying out the polymerization substantially below the critical homogeneous polymerization temperature results in catastrophic gel formation.

EXAMPLE 3 The experiment of Example 2 was repeated at 105" C. and 110 C. At 110 C. the polymer formed Was highly gelled. The results at 105 C. are shown in Table 11.

TABLE IL-BULK POLYMERIZATION OF A 30 VOLUME PERCENT ISOP RENE FEED AT 100 C.

Percent Polymer Reaction time yield (g) Conversion Gel content It is apparent that at low conversions at a temperature slightly below the CHPT low gel content polymer may be formed. At higher conversions, however, gel content increases to unacceptable levels.

EXAMPLE 4 The polymerization of Example 2 was repeated at C. using 26.7 ml. of monomer and varying amounts of catalyst solution (0.5-2.0 ml.). After deactivating the catalyst the unreacted monomers and polymer were cooled to C. Precipitation of polymer resulted. Warming of the reactant polymer system to 100 C. redissolved the polymer. Hence, the polymer formed was not gelled. Therefore, it is demonstrated that precipitation of the polymer is a result of reduced temperature and that gel formation only occurs in the presence of active catalyst.

It is apparent, therefore, that precipitation of polymer during polymerization is not a result of gelation but that gelation is the result of precipitation of polymer in the presence of active catalyst. Hence, it is essential to carry out the process of this invention in a homogeneous system to avoid gelation.

EXAMPLE 5 The polymerization reactions of Example 1 were repeated at the CHPT for various feed compositions and the molecular weights of the product determined. Number average molecular weights (Mn) were determined by membrane osmometry and viscosity average molecular weights were determined in toluene at 25 C. The results are shown in Table IV.

TABLE IV. Mn AND Tdv FOR BULK POLYMERIZATION POLYMERS AT CHPT It is apparent that in a bulk polymerization at the lowest possible polymerization temperature yielding substantially gel-free products (CHPT) high number average molecular weight polymers (Mn 120,000) cannot be prepared.

The polymers so formed, although gel-free and high in unsaturation, do not have a number average molecular weight (fin) of at least 120,000.

In order to produce higher molecular weight gel-free products it is necesary to reduce the polymerization temperature while at the same time maintaining the reactants and polymer in solution. This is accomplished by using at least five to about 40 weight percent cosolvent.

EXAMPLE 6 The experiments of Example 5 were repeated using various cosolvents and varying the percent isoprene in the feed from about 5 to about 38 vol. percent. The results are shown in Table V. Use of a cosolvent permits lower polymerization temperature and gives polymers having number average molecular weights of at least 120,000, whereas, for example, a monomer feed containing 15 vol. percent isoprene had a CHPT of 85 C. The addition of inert solvent permits the polymerization to be carried out at 120 to C. with significant increases in fin values, i.e., at least 120,000.

For a given isoprene/isobutylene ratio the amount of solvent used will affect molecular weight.

The polymers formed were substantially gel free (e.g., less than 1.0%). Although prior art butyl rubbers are said to contain unsaturation as essentially 1,4-enchainment, the products of this invention contain significant quantities of 1,2- and 3,4-enchainment.

Hence, it is apparent from these data that at least 5 vol. percent solvent is necessary to avoid gel formation depending on the cosolvent used and that more than 40 vol. percent solvent results in Mn values of less than TABLE V.ISOBUTYLENE-ISOPRENE COPOLYMERIZATIONS USING COSOLVENTS (120 C.)

Feed (volume Percent Mole, perpercent Vol. el cent unset. lsoprene) Solvent percent 1 lI/InXlO b1] MVX10 content (infrared) 10 n-Heptane 20 295 0. 98 6. 15 CS2 20 172 1. 340 412 0.38 a 14. 4 15 n-Heptane. 20 187 1. 137 318. 8 -0 12. 0 15 Methylcyclo 10 197 1. 288 384. 6 0.26 30 CS; 162 1. 342 315. 2 0. 56 30 Cyclohexane. 7. 5 198. 0. 52 30 do 20 172 1. 356 320 0. 69 30 n-Heptane. 182 1. 386 331 0. 92 31. 8 30 n-Pentane 7. 5 160 1. 056 220 0. 71 38 n-Heptene- 5 157 1. 397 281 0. 39 42. 2 4 CS; 181 1. 455 355 0. 37 16. 4

1 Uncorrected for volume decrease on cooling. 1 0.1% in toluene at C. I NMR analysis. 4 -130 C.

EXAMPLE 7 The minimum inert cosolvent requirement was determined for various cosolvents and isoprene contents. The approximate cosolvent required was estimated from the extrapolated curve (broken line) of FIG. 1. The comshown in Table VI.

120,000 regardless of the multiolefin content or the solvent selected.

The data is represented graphically in FIG. 2. It is evident that the quantity of solvent used is critical since TABLE VI.-MINIMUM INERT COSOLVENT REQUIREMENTS FOR ISOPRENE-ISOBUTYLENE SYSTEMS Estimated Actual minimum cosolvent required Polymerl- (vol. percent) zation solvent temperrequire- Methyl- Isoprene content ature ment (vol. 150- n-Hepcyclo- (vol. percent) 0.) percent) pentane tane hexane CS:

It is apparent that minimum cosolvent requirements for a homogeneous polymerization are a function of both polymerization temperature and the solvent selected. The values estimated by the manner described earlier from FIG. 1 are good first approximations of the solvent requirements.

EXAMPLE 8 The elfect of cosolvent on Mn was determined for various isobutylene-isoprene systems. The polymerization was carried out in the manner of Example 1 at 120 C. using AlCl in CH Cl as the catalyst. The results are shown in Table VII.

TABLE VII.EFFECT OF COSOLVEN'I ON NUMBER AVER- AGE MOLECULAR WEIGHT Isoprene content Cosolventl (vol. percent) vol. percent Mn UV 082/ 5 Gel CS2 CS2/7.5

1 n-C5=n-pentane. I-C =lsopentane. i MCH=methy1cyclohexane.

too little inert cosolvent results in gel formation; too great a quantity of cosolvent results in reduction of Mn below 120,000.

EXAMPLE 9 EXAMPLE 10 The eifect of polar solvent on catalysis was evaluated by carrying out polymerization in the manner of Example I using 21 B15 isobutylene-isoprene feed in conjunction with 20 volume percent cosolvent based on the monomer plus cosolvent of heptane as cosolvent using polar and non-polar catalyst solvents. The results are tabulated in Table VIII.

TABLE VIIL-EFFECT OF POLAR SOLVE1;IV%IF(TCATALYSTS ON PRODUCT MOLECULAR Catalyst 1 Unsatura- Catalyst concen- Temp., tlon (mole Run No. B No. Catalyst solvent tration 0. Mn Mv percent) 1.5 AlBra n-Heptane 0.45 410,000 1.4

1.5 AlBr -.---do 0.45 581,000 1. 1

15 AlBra 0. 45 57,000

15 AlBra 0. 45 177, 000 11. 6

15 A1Bl'3 0.58 157, 000

15 AlBra 0.34 2, 9.8

1 30 AlBra n-Heptane. 0. 45

l Grams catalyst per 100 ml. of catalyst solvent. 1 10 vol. percent cosolvent. Semi-liquid; very low molecular weight.

It is evident from the data of Table VIII that although non-polar catalyst solvents may be used to carry out polymerizations the product is low in number average molecular weight. For example, Run 4 was carried out using heptane as the catalyst solvent. The product had a mole percent unsaturation of 11.6. However, the number average molecular weight was only 72,000. By comparison, when CH Cl was substituted for heptane as the catalyst solvent (Run 6) the product had a number average molecular weight of 251,000. Hence, in order to produce polymers both high in unsaturation and Mn it is necessary to use a polar solvent as the catalyst solvent. AlBr was used as a catalyst in the comparative studies since AlCl is insoluble in non-polar media and results in gelation.

EXAMPLE 11 It is essential that the catalysts of this invention be dissolved in the polar solvent prior to introduction into the reaction medium. To illustrate this point, the experiments of Example were repeated for a BIS feed using AlBr as the catalyst and heptane as the cosolvent and CH Cl or cyclohexane as the catalyst solvents. In order to have fully comparative results where the catalyst solvent was essential in the preparation of the high Mn polymers of this invention.

EXAMPLE 13 EXAMPLE 14 An isobutylene-cyclopentadiene monomer blend comprising about 5 vol. percent cyclopentadiene and about 20 vol. percent CS based on total monomer pl-us CS; was polymerized in the monomer of Example 13 at a ltemperature of =120 C. The product had a Mn of 204,000 and was comprised of 16 mole percent of the cyclopentadiene.

not used to dissolve catalyst, it was added to the cosol- EIQAMPLE 15 vent. Example 14 was repeated utilizing methylcyclohexane TABLE IX.EFFECT OF ADDING CATALYST SOLVENT TO COSOLVENT Catalyst Cosolvent/ Unsaturasolution, Catalyst solventin monomer tion (mole Run No. Catalyst solvent (mL) cosolvent (ml.) (ml.) Mn percent) 1 Methyl chloride"..- 20 None /200 251,000 9,8 2 Cyclohexane 20 -....-d0 50/200 69,000 3..-- Methyl chloride..." 25 Cyclohexane (25) 25/200 173,000 12.6 4 Cyelohexane 25 Methyl chloride (25)....- 25/200 68,000

A comparison of Runs 1 and 2 Show that use of Polar 50 instead of CS as the cosolvent. The product had a Mn catalyst solvent results in high Mn where non-polar catalyst solvent results in low Mn.

A comparison of Runs 3 and 4 shows that despite the fact the composition of the reaction medium is the same addition of the polar solvent to the cosolvent rather than using it as a catalyst solvent does not give the same high Mn that is achieved by predissolving the catalyst in polar solvent. Hence, in order to produce polymers of high Mn, it is essential that the catalyst be predissolved in the polar solvent rather than merely dissolving the catalyst in a solvent and adding the polar solvent to the reaction medium.

EXAMPLE 12 The procedure of Example 10 was employed in an attempt to prepare isobutylene-isoprene copolymers from B15 feeds using Friedel-Crafts catalyst other than aluminum halides. The following catalyst solutions were used for catalyst: BF in CHgCl, TiCl in heptane, TiCl in CH CI, TiCl /trichloroacetic acid (2:1) in heptane, TiCl /trichloroacetic acid (2: l) in CH Cl, SbF in CH Cl and S'bF in heptane.

The resulting polymers were low in Mn, i.e. less than 120,000. Hence, it is apparent that proper selection of the Friedel-Crafts catalyst namely aluminum halides is of 194,000. Analysis of the isobutylene copolymer indicated that it was comprised of 16 mole percent cyclopentadiene.

EXAMPLE 16 Example 14 was repeated utilizing a monomer blend comprising 7% cyclopeutadiene. The product had a Mn of 163,000. Analysis of the copolymer indicated that it was comprised of 24 mole percent cyclopentadiene.

Various other experiments were carried out in a similar manner. The data is tabulated in Table X.

TABLE X.ISOBUT YLENE-C YOLOPENTADIENE Polymerization at C.

2 Volume of isobutylene, cyclopentadlene and cosolvent measured at -120, -78 and 25 C. respectively.

3 NMR analysis.

19 It is evident that the process of this invention may be used to prepare substantially gel-free high Mn copolymers of cyclopentadiene. Surprisingly, the proportion of CPD in the polymer is greater than its proportion in the monomer.

EXAMPLE 17 A terpolymer of isobutylene isoprene and cyclopentadiene was prepared using the process of this invention. The reaction was carried out at 120 C. with a monomer mix comprising 2856 ml. isobutylene, 336 ml. isoprene and 168 ml. of cyclopentadiene; 840 ml. of methylcyclohexane was used as the inert solvent and A101 (0.62 g. A1Cl /100 m1. CH Cl) as the catalyst.

The product had a Mn of 180,000 and was comprised of 8 mole percent isoprene and 18.7 mole percent cyclopentadiene. The gel content was less than 0.6%.

EXAMPLE 1 8 The polymers of Example 19 were formulated as follows:

100 parts Polymer: by weight Zinc stearate 1.65 HAF carbon black 60 Hydrocarbon oil plasticizer 1 20 Antioxidant 2 1.11 Zinc oxide Sulfur 2.5 Sulfenamide accelerator 3 0.75

1 Flexon 845 ASTM Type 4 'lhermoflex A; 50% N-plienyl-beta-naphthylamlno; 25%

g, p'-dimethoxy-diphenyl amine; 25% diphenyl-p-phenylene 1am ne.

igantocure NS; N-tertiary butylbenzothiazole-2-sulfenam e.

The samples were vulcanized under varying conditions. The results are depicted graphically in FIG. V wherein tensile strength is plotted as a function of Mn. It is apparent that tensile strength increases rapidly with Mn and approaches an asymptotic value at about 120,000 'Mn.

Data for polymers of various Mn is tabulated in Table XI. US. Government specifications for isoolefin-isoprene copolymer (butyl rubber) are presented for comparison.

It is noted that only copolymers having Mn of at least 120,000 achieve the necessary high tensile without loss of elasticity (extension set). Heretofore, it was not possible to produce polymers meeting these specifications having high unsaturation, i.e. at least 5 mole percent unsaturation.

EXAMPLE 21 Copolymers of isobutylene and isoprene of difierent isoprene content were prepared and their permeability to air determined according to the method described by M. Czuha, Rubber World, May 1954. The subject copolymers were compared to butyl rubber and to natural rubber for permeability to air at 150 F. Suitable membrane specimens were prepared by press molding and tested in a Warburg-type apparatus. The compositions were of technological quality containing 50 parts of carbon black and appropriate crosslinking agent. The results are shown in FIG. 6. The permeability value Q is defined as the number of cubic feet of air at standard conditions which penetrates through a 0.001 inch thickness of membrane under a pressure diiferential of '1 lb. per sq. in. per sq. foot of surface per day.

The results in F110. 6 clearly demonstrate that rather high levels of unsaturation (isoprene) can be incorporated into the copolymer with little change in permeability. Above approximately 40% isoprene content, permeability increases rapidly with increasing isoprene. Thus, considerable vulcanization flexibility due to increased unsaturation can be realized without significantly sacrificing impermeability characteristics.

EXAMPLE 22 The air permeability studies of Example 21 were repeated using isobutylene-conjugated diene copolymers and terpolymers. A comparison of air permeability as a function of diene content for acyclic and cyclic dienes in addition to terpolymers of acyclic and cyclic dienes is shown in FIG. VllI. The terpolymers shown are isobutyleneisoprene-CPD and isobutylenepiperylene-CPD wherein the isoprene content (or piperylene content) is 8 mole percent and the CPD content is 18.7 mole percent.

It is evident that the cyclic diene result in polymers having improved (lower) air permeability, e.g., better than conventional butyl rubbers. Surprisingly, air permeability decreases with increasing cyclic diene content. Unexpectedly, replacing a portion of the cyclic diene with an acyclic diene (terpolymer) result in no significant deleterious effect on air permeability.

EXAMPLE 23 Various polymers were tested for ozone degradation by determining their resistance to cracking when exposed to ozone. Test conditions conformed to ASTM D1149- T specification. Higher ozone levels and strains were employed than cutomarily utilized for butyl rubber. All elastomers were cured to the same crosslink density. The results are shown in Table XII.

TABLE XL-EFFECT OF NUMBER-AVERAGE MOLECULAR WEIGHT ON THE STRESS-STRAIN PROPERTIES OF AN ISOBUTYLENE-ISOPRENE COPOLYMER COMPOSITION 1 Constant erosslinking time: 20 minutes at 300 F.

1 Test compound: Polymer 100, antioxidant 1.1, zinc stearate 1.65, HAF carbon black 60, hydrocarbon plasticizer 20, zinc oxide 5, sulfur 2.5, sulfenamide accelerator (Santocure NS) 0.75. Polymer composition: isobutylene; isoprene.

2 U.S. Government specification 221-ZZ50C (Mar. 6, 1968) for butyl rubber.

Membrane osmometry-toluene solutions a TABLE XII.OZONE CRACKING F COPOLYMERS AND CONTROLS A'I 122 F. USING 100 PARTS PER 100 MILLION OZONE ENVIRONMENT 1 Hours to Percent first Final Sample Polymer unsaturation cracks 1 condition 1 Enjay Butyl 035 (butyl rubber) 1 240 Broken 456 hours. 2 Isobutylene CPD copolymer 3"-.. 1, 056 No cracking when test terminated. 3 J 1,056 Do. 4 Isobutylene-CPD-isoprene terpolymer. 18 CPD; 8 isoprene 1, 056 Do.

1 Orceo Company ozone chamber.

2 Samples under 2025% strain first 168 hrs.; -35% strain after 216 hrs.; and -50% strain after 312 hrs.

EXAMPLE 24 Various isobutylene copolymers were tested for ozone resistance by the method of Example 23. The results are tabulated in Table XIII.

having a mole percent unsaturation of about 12 and a Mn of about 160,000 was compounded as follows:

Copolymer: 100 parts by weight Zinc oxide 5.0 Stearic acid 1.0 Sulfur 1.5

Antioxidant 1 0.75 Accelerators 2 1.0

1 Thermoflex A. 2 N-tertiarybutylbenzothiazole-Z-sulfenamlde.

An activator (0.5 part diphenyl guanidine) and a retarder (0.5 part N-nitroso-diphenylamine) were added to TABLE XIII.OZONE CRACKING OF COPOLYMERSEAND CONTROLS AT 122 F. USING 50 PARTS PER 100 MILLION OZONE NVIRONMENT Hours to first Sample Polymer Unsaturation cracks Final condition 1 Enjay Buty1035 -1% isoprene 383 Broken-1,055 hours. 2.- Eniay Butyl 268 -2% 1soprene 215 Broken-479 hours. 3.. Isobutylene-isoprene-copolymer 12% 1s oprene 6 Broken-73 hours. 4 Isobutylene-piperylene copolymer 12% p1perylene 22 Broken-143 hours. 5- Isobutylene-cyclopentadiene copolymer 20 CPD 1,233 Test terminated-mo cracking 6 Isobutylene-isoprene-cyclopentadiene terpolymer 18% CPD; 8% isoprene. 1, 233 Do.

It is evident that for isoprene copolymers resistance 35 EXAMPLE 25 The versatility of sulfenamide accelerators for crosslinking elastomers resides in their ability to be modeled to the best advantage for a particular use. These systems which are well known in the art for for use with the highly unsaturated general purpose elastomers cannot be used with butyl rubbers which require ultra-accelerators due to their low level of unsaturation. With ultra-accelerators, formulations must be compounded below the vulcanization temperature which often must be dangerously close to the vulcanization temperature and premature vulcanization (scorch) is frequently troublesome.

The sulfenamide systems can be operated with delayed action at the actual temperature of vulcanization and the scorch problem is completely eliminated. These systems are characterized by a distinct delay period during which no vulcanization occurs followed by rapid crosslinking to an asymptotic level of crosslink concentration. The delay period is important to the processing safety required in hot processing operations common to elastomer commerce.

It is a further advantage of these curatives that in common use the delay times are are shortened or lengthened by the addition of activators or retarderswithout significantly affecting the shape of the crosslinking curves and rapid curing to the same high level of crosslink density occurs regardless of delay time.

An isobutylene-isoprene copolymer of this invention various blends to control cure rate. Vulcanization was carried out at 290 F. The results are shown in FIG. VIII.

It is evident that the delay time may be varied by controlling the amount of activator or retarder added. Delay times may be varied from zero to a few hours while total cure times may be varied from less than ten minutes to more than one hour. Such versatility of cure rate is not possible with the low unsaturation isoolefin-multiolefin copolymers of commerce.

EXAMPLE 26 The experiment of Example 25 was repeated with a copolymer having a number average molecular weight of 158,000 and containing 20% cyclopentadiene. The delay time in vulcanization at 290 F. was 55 minutes after which the rate and extent of crosslinking was similar to that shown in FIG. VIII. Activation with '10 part of diphenylguanidine reduced the delay time to 30 minutes. Retardation with 0.25 part of N-nitroso-diphenylamine increased the delay time to 70 minutes.

EXAMPLE 27 The experiment of Example 26 was repeated with a copolymer having a number average molecular weight of 171,000 and containing 12% of piperylene. The results were similar to those obtained with the cyclopentadine copolymer.

EXAMPLE 28 The experiment of Example 20 was repeated with a terpolymer of number average molecular weight of 166,- 000 and containing 8% of isoprene and 18% cyclopentadiene. The delay time was 25 minutes at 290 F. Activation with 0.5 part of diphenylguanidine reduced the delay time to 5 minutes 290 F. Retardation with 0.5 part of N-nitroso-diphenylamine increased the delay time to 50 minutes at 290 F. 

